JP2011040282A - All-solid secondary battery - Google Patents
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Abstract
Description
この発明は、電気自動車用電池や大型蓄電池として利用可能な全固体二次電池に関するものである。 The present invention relates to an all-solid-state secondary battery that can be used as a battery for an electric vehicle or a large-sized storage battery.
近時、電解質として有機溶媒にリチウム塩を溶解させた非水電解液が用いられた従前のリチウムイオン二次電池に比べて安全性が高い電池として、リチウムイオン伝導体である無機固体電解質を用いた全固体リチウムイオン二次電池が注目されている。 Recently, an inorganic solid electrolyte, which is a lithium ion conductor, has been used as a battery that is safer than conventional lithium ion secondary batteries that use a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent. The all-solid-state lithium ion secondary battery has been attracting attention.
全固体二次電池においても、従来の電解液を用いた二次電池で使用されている、ＬｉＣｏＯ２（以下、ＬＣＯとも言う。）からなる正極活物質を用いた検討が行われているが、全固体二次電池において課題となっている正極活物質と固体電解質との界面の抵抗を減少させるために、主に、ＬＣＯ表面を他の物質で被覆処理して抵抗を減少させることが検討されている（特許文献１）。更に、固体電解質と正極活物質との反応を抑制するために、固体電解質と正極活物質とに同アニオン種を含む化合物を組み合わせて用いる試みや（特許文献２）、固体電解質を薄膜化することにより正極活物質と固体電解質との抵抗を低減する試みもなされている（特許文献３）。 In all solid state secondary batteries, studies using a positive electrode active material made of LiCoO 2 (hereinafter also referred to as LCO), which is used in secondary batteries using conventional electrolytes, are being conducted. In order to reduce the resistance at the interface between the positive electrode active material and the solid electrolyte, which is an issue in all-solid-state secondary batteries, it has been studied mainly to reduce the resistance by coating the LCO surface with other materials. (Patent Document 1). Furthermore, in order to suppress the reaction between the solid electrolyte and the positive electrode active material, an attempt to use a compound containing the same anionic species in the solid electrolyte and the positive electrode active material (Patent Document 2), or thinning the solid electrolyte Attempts have also been made to reduce the resistance between the positive electrode active material and the solid electrolyte (Patent Document 3).
全固体二次電池では、電極内部に混在させる固体電解質と活物質との固体−固体間の接触性が、固体電解質と活物質との界面の抵抗の大小に大きく関わってくる。そのため、固体電解質と混合し加圧した後の正極活物質の粉体の状態が、全固体二次電池の電流の取り出し易さ、すなわち出力特性に影響を与えると考えられる。 In an all-solid-state secondary battery, the solid-solid contact property between the solid electrolyte and the active material mixed inside the electrode greatly affects the resistance of the interface between the solid electrolyte and the active material. Therefore, it is considered that the state of the positive electrode active material powder after being mixed and pressurized with the solid electrolyte affects the ease of taking out the current of the all-solid secondary battery, that is, the output characteristics.
正極活物質が粒径が大きな単分散状態の一次粒子からなる場合は、固体電解質と正極活物質との接触点が少ないので、電子及びリチウムイオンの移動経路を充分に確保することは困難である。一方、正極活物質が粒径が小さな単分散状態の一次粒子からなる場合は、粒子の比表面積は大きくなるが、固体電解質と正極活物質との界面が増加することによって逆に抵抗上昇に繋がる。また、正極内に空隙が増加することによって、正極の電極密度が低下するので、これによっても正極の内部抵抗が上昇する。従って、単分散状態の一次粒子の粒径を小さくすることによっては、電池のインピーダンスを下げることはできない。 When the positive electrode active material is composed of primary particles having a large monodispersed state, there are few contact points between the solid electrolyte and the positive electrode active material, so it is difficult to secure a sufficient movement path for electrons and lithium ions. . On the other hand, when the positive electrode active material is composed of monodispersed primary particles with a small particle size, the specific surface area of the particles is increased, but the increase in the interface between the solid electrolyte and the positive electrode active material leads to an increase in resistance. . Moreover, since the electrode density of a positive electrode falls by the space | gap increasing in a positive electrode, this also raises the internal resistance of a positive electrode. Therefore, the impedance of the battery cannot be lowered by reducing the particle size of the primary particles in the monodispersed state.
また、合成時に１０００℃近くの高温で焼成したり、フラックス等を添加して溶融させたりした、粒径が大きな単分散状態の一次粒子からなる正極活物質は、粒子自体が非常に硬く、割れ難い材料であり、更に、割れるような高い圧力をかけた際には、粒子が均等に割れるのではなく、微細な欠片が発生したり、大きな空隙が生じたりする。このような欠片は、固体電解質と正極活物質との間の空隙を埋めることはできず、また、新規な表面を持つので反応が活性な状態になる。そのため不均一な反応が起こり、固体電解質と正極活物質との界面の抵抗を低減することは困難である。また、新たに生じた空隙は、リチウムイオンや電子の移動経路を妨げるので、固体電解質と正極活物質との界面の抵抗上昇に繋がり、電池の出力特性の改善には繋がらない。 In addition, the positive electrode active material composed of primary particles having a large monodispersed state, which is fired at a high temperature close to 1000 ° C. at the time of synthesis or melted by adding a flux or the like, is very hard and cracks. Further, it is a difficult material, and when a high pressure that can be broken is applied, the particles are not evenly cracked, but fine fragments are generated or large voids are generated. Such a piece cannot fill the gap between the solid electrolyte and the positive electrode active material, and has a novel surface, so that the reaction becomes active. Therefore, a non-uniform reaction occurs, and it is difficult to reduce the resistance at the interface between the solid electrolyte and the positive electrode active material. In addition, the newly generated voids obstruct the movement path of lithium ions and electrons, leading to an increase in resistance at the interface between the solid electrolyte and the positive electrode active material, and not improving the output characteristics of the battery.
そこで本発明は、上記現状に鑑み、出力特性及びサイクル特性に優れた全固体二次電池を提供することを課題とする。 In view of the above, the present invention has an object to provide an all-solid-state secondary battery excellent in output characteristics and cycle characteristics.
すなわち本発明に係る全固体二次電池は、負極と、リチウムイオン伝導率が１０−４Ｓ／ｃｍ以上である無機固体電解質を含有する固体電解質層と、一次粒子が凝集した二次粒子からなる正極活物質及び前記無機固体電解質を含有する正極とを備えていることを特徴とする。 That is, the all-solid-state secondary battery according to the present invention includes a negative electrode, a solid electrolyte layer containing an inorganic solid electrolyte having a lithium ion conductivity of 10 −4 S / cm or more, and secondary particles in which primary particles are aggregated. A positive electrode active material and a positive electrode containing the inorganic solid electrolyte are provided.
このようなものであれば、正極活物質として一次粒子が凝集した二次粒子からなるものを用いることにより、正極内部や固体電解質質と正極との界面において、正極活物質と固体電解質との接触性が高まるので、正極活物質と固体電解質との間における電子及びリチウムイオンの移動経路が確保され、正極活物質と固体電解質との界面における抵抗上昇を抑制することができる。また、このような正極活物質を用いることにより、正極活物質と固体電解質との間に空隙が生じにくく、正極の電極密度を向上することができるので、正極内部における電子及びリチウムイオンの移動経路も確保され、正極の内部抵抗が低下し、電池の出力特性を改善することが可能である。 In such a case, by using a secondary particle in which primary particles are aggregated as a positive electrode active material, contact between the positive electrode active material and the solid electrolyte is performed in the positive electrode or at the interface between the solid electrolyte and the positive electrode. Therefore, the movement path of electrons and lithium ions between the positive electrode active material and the solid electrolyte is secured, and an increase in resistance at the interface between the positive electrode active material and the solid electrolyte can be suppressed. Further, by using such a positive electrode active material, it is difficult to generate a gap between the positive electrode active material and the solid electrolyte, and the electrode density of the positive electrode can be improved. Is ensured, the internal resistance of the positive electrode is lowered, and the output characteristics of the battery can be improved.
前記正極活物質は、一次粒子の平均粒径が１μｍ以下であり、二次粒子のメジアン径が５μｍ以上であるものが好ましい。 The positive electrode active material preferably has an average primary particle size of 1 μm or less and a median diameter of secondary particles of 5 μm or more.
前記正極活物質は、電池製造時のプレスによって二次粒子の凝集が崩壊しやすいものが好ましく、具体的には、３ｔ／ｃｍ２の圧力で加圧した際の、加圧前後の二次粒子のメジアン径の変化率｛１００−（加圧後のメジアン径／加圧前のメジアン径）×１００｝が、１５％以上であるものが好ましい。 The positive electrode active material is preferably a material in which aggregation of secondary particles tends to collapse due to pressing during battery production, specifically, secondary particles before and after pressing when pressed at a pressure of 3 t / cm 2. The median diameter change rate {100− (median diameter after pressurization / median diameter before pressurization) × 100} is preferably 15% or more.
このような構成の本発明によれば、正極内部や正極と固体電解質層との界面において、正極活物質と固体電解質との間の空隙を低減させることができ、更に、一次粒子が小さいので、リチウムイオンの拡散速度も速く、固体電解質との接触点も多くなり、リチウムイオン及び電子の移動経路が保持され、正極の内部抵抗や、正極と固体電解質層との界面抵抗の低減が可能となり、全固体二次電池の出力特性やサイクル特性を向上することが可能となる。 According to the present invention having such a configuration, voids between the positive electrode active material and the solid electrolyte can be reduced inside the positive electrode or at the interface between the positive electrode and the solid electrolyte layer, and further, since the primary particles are small, The diffusion rate of lithium ions is fast, the number of contact points with the solid electrolyte increases, the movement path of lithium ions and electrons is maintained, and the internal resistance of the positive electrode and the interface resistance between the positive electrode and the solid electrolyte layer can be reduced. It becomes possible to improve the output characteristics and cycle characteristics of the all-solid-state secondary battery.
以下、本発明の一実施形態に係る全固体二次電池について説明する。 Hereinafter, an all solid state secondary battery according to an embodiment of the present invention will be described.
本実施形態に係る全固体二次電池は、正極、負極、及び、正極と負極に挟まれた固体電解質層からなるものである。 The all solid state secondary battery according to the present embodiment includes a positive electrode, a negative electrode, and a solid electrolyte layer sandwiched between the positive electrode and the negative electrode.
前記正極は、一次粒子が凝集した二次粒子からなる正極活物質と、後述する無機固体電解質とを含有するものである。 The positive electrode contains a positive electrode active material composed of secondary particles in which primary particles are aggregated and an inorganic solid electrolyte described later.
図１（ａ）に示すように、正極活物質が粒径が大きな単分散状態の一次粒子からなる場合、リチウムイオンの拡散速度が遅く、また、正極活物質粒子自体が硬く割れにくいので、固体電解質との接触点が少なく、電子及びリチウムイオンの移動経路を充分に確保することは困難である。また、図１（ｂ）に示すように、正極活物質が粒径が小さな単分散状態の一次粒子からなる場合、粒子の比表面積は大きくなるが、固体電解質と正極活物質との界面が増加することによって逆に抵抗上昇に繋がる。また、固体電解質と正極活物質との間に空隙が増加し、正極の電極密度が低下するので、電子及びリチウムイオンの移動経路を充分に確保することが困難になり、これによっても正極の内部抵抗が上昇する。 As shown in FIG. 1A, when the positive electrode active material is composed of primary particles having a large particle size, the diffusion rate of lithium ions is slow, and the positive electrode active material particles themselves are hard and difficult to break. There are few contact points with an electrolyte, and it is difficult to secure a sufficient movement path for electrons and lithium ions. In addition, as shown in FIG. 1B, when the positive electrode active material is composed of primary particles having a small particle size, the specific surface area of the particles is increased, but the interface between the solid electrolyte and the positive electrode active material is increased. By doing so, the resistance rises. In addition, since voids increase between the solid electrolyte and the positive electrode active material and the electrode density of the positive electrode decreases, it becomes difficult to secure a sufficient movement path for electrons and lithium ions, and this also causes the inside of the positive electrode Resistance rises.
これに対して、本発明では、図１（ｃ）に示すように、正極活物質が一次粒子の凝集した二次粒子からなるので、固体電解質との接触点が多くなり、また、二次粒子が崩壊しても、その間隙は新たな二次粒子で埋められるので、正極の電極密度も高くなり、電子及びリチウムイオンの移動経路を充分に確保することができる。 In contrast, in the present invention, as shown in FIG. 1 (c), the positive electrode active material is composed of secondary particles in which primary particles are aggregated, so that the number of contact points with the solid electrolyte increases, and the secondary particles Even if collapses, since the gap is filled with new secondary particles, the electrode density of the positive electrode is increased, and a sufficient movement path for electrons and lithium ions can be secured.
本発明で用いられる正極活物質としては、一次粒子の平均粒径が１μｍ以下であり、二次粒子のメジアン径が５μｍ以上であるものが好ましく、より好ましくは、一次粒子の平均粒径が０．１〜１μｍであり、二次粒子のメジアン径が５〜２０μｍである。一次粒子の平均粒径が１μｍより大きいと、リチウムイオンの拡散速度が遅くなり、固体電解質との接触点も減少する傾向にある。また、二次粒子のメジアン径が５μｍより小さいと、二次粒子間の空隙が増加し、正極の電極密度が低下しやすく、また、固体電解質との接触点も減少する傾向にある。 As the positive electrode active material used in the present invention, those having an average primary particle diameter of 1 μm or less and a median diameter of secondary particles of 5 μm or more are preferable, and more preferably, the average particle diameter of primary particles is 0. 0.1 to 1 μm, and the median diameter of the secondary particles is 5 to 20 μm. When the average particle size of the primary particles is larger than 1 μm, the diffusion rate of lithium ions becomes slow, and the contact point with the solid electrolyte tends to decrease. On the other hand, if the median diameter of the secondary particles is smaller than 5 μm, voids between the secondary particles increase, the electrode density of the positive electrode tends to decrease, and the contact point with the solid electrolyte tends to decrease.
なお、本発明における一次粒子の平均粒径は、走査型電子顕微鏡（ＳＥＭ）で観察した複数の一次粒子の粒径を平均することにより求めることができ、一方、本発明における二次粒子のメジアン径は、粒度分布計により得られた粒度分布のＤ５０から求めることができる。 The average particle diameter of the primary particles in the present invention can be obtained by averaging the particle diameters of a plurality of primary particles observed with a scanning electron microscope (SEM), while the median of the secondary particles in the present invention. The diameter can be obtained from D50 of the particle size distribution obtained by the particle size distribution meter.
前記正極活物質として具体的には、例えば、ＬｉＮｉｘＭ１ｙＭ２ｘＯ２（０．５＜ｘ＜０．９、０．１＜ｙ＜０．６、０．０１＜ｚ＜０．４、Ｍ１はＣｏ及び／又はＭｎ、Ｍ２はＡｌ、Ｍｇ、Ｔｉ、Ｍｎの内一種以上）、ＬｉＣｏＯ２等が用いられる。これらの正極活物質は、単独で用いられてもよく、二種以上が併用されてもよい。 Specific examples of the positive electrode active material include LiNi x M1 y M2 x O 2 (0.5 <x <0.9, 0.1 <y <0.6, 0.01 <z <0.4. M1 is Co and / or Mn, M2 is at least one of Al, Mg, Ti, and Mn), LiCoO 2 and the like. These positive electrode active materials may be used independently and 2 or more types may be used together.
本発明で用いられる正極活物質としては、更に、電池製造時のプレスによって二次粒子の凝集が崩壊しやすいものが好ましく、具体的には、３ｔ／ｃｍ２の圧力で加圧した際の、加圧前後の二次粒子のメジアン径の変化率｛１００−（加圧後のメジアン径／加圧前のメジアン径）×１００｝が、１５％以上であるものが好ましく、より好ましくは１５〜２０％である。このようなものであれば、固体電解質と正極活物質との間に空隙が生じにくい。 As the positive electrode active material used in the present invention, a material in which the aggregation of secondary particles is likely to be disintegrated by pressing during battery production is preferable, and specifically, when pressurized at a pressure of 3 t / cm 2 , The change rate of the median diameter of the secondary particles before and after pressurization {100- (median diameter after pressurization / median diameter before pressurization) × 100} is preferably 15% or more, more preferably 15 to 20%. If it is such, it is hard to produce a space | gap between a solid electrolyte and a positive electrode active material.
前記負極は、リチウムとの合金化や、リチウムの吸蔵、放出が可能な負極活物質を含有するものである。当該負極活物質としては特に限定されず、例えば、リチウム、インジウム、スズ、アルミ、ケイ素等の金属やそれらの合金：Ｌｉ４／３Ｔｉ５／３Ｏ４、ＳｎＯ等の遷移金属酸化物：人造黒鉛、黒鉛炭素繊維、樹脂焼成炭素、熱分解気相成長炭素、コークス、メソカーボンマイクロビーズ（ＭＣＭＢ）、フルフリルアルコール樹脂焼成炭素、ポリアセン、ピッチ系炭素繊維、気相成長炭素繊維、天然黒鉛、難黒鉛化性炭素等の炭素材料等が挙げられる。これらの負極活物質は、単独で用いられてもよく、二種以上が併用されてもよい。 The negative electrode contains a negative electrode active material capable of being alloyed with lithium, occluded and released from lithium. The negative electrode active material is not particularly limited, and examples thereof include metals such as lithium, indium, tin, aluminum, and silicon, and alloys thereof: transition metal oxides such as Li 4/3 Ti 5/3 O 4 and SnO: artificial Graphite, graphite carbon fiber, resin-fired carbon, pyrolysis vapor-grown carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, Examples thereof include carbon materials such as non-graphitizable carbon. These negative electrode active materials may be used independently and 2 or more types may be used together.
前記正極及び負極は、上述の活物質からなる粉末に、例えば、導電剤、結着剤、フィラー、分散剤、イオン導電剤等の添加剤が、適宜選択されて配合されていてもよい。 For the positive electrode and the negative electrode, additives such as, for example, a conductive agent, a binder, a filler, a dispersant, and an ionic conductive agent may be appropriately selected and blended with the powder made of the above active material.
前記導電剤としては、例えば、黒鉛、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維、金属粉等が挙げられ、前記結着剤としては、例えば、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリエチレン等が挙げられる。更に、前記負極にも、後述する無機固体電解質が配合されていてもよい。 Examples of the conductive agent include graphite, carbon black, acetylene black, ketjen black, carbon fiber, and metal powder. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, and polyethylene. Is mentioned. Furthermore, the inorganic solid electrolyte mentioned later may be mix | blended with the said negative electrode.
前記正極又は負極を製造するには、例えば、上述の活物質と各種添加剤との混合物を作製し、ペレット状にして油圧プレス機により厚密化して、正極又は負極とする方法や、水や有機溶媒等の溶媒に添加してスラリー又はペースト化し、得られたスラリー又はペーストを、ドクターブレード法等を用いて集電体に塗布し、乾燥し、圧延ロール等で圧密化して、正極又は負極とする方法がある。 In order to produce the positive electrode or the negative electrode, for example, a mixture of the above-described active material and various additives is prepared, formed into a pellet and thickened by a hydraulic press machine to obtain a positive electrode or a negative electrode, water, It is added to a solvent such as an organic solvent to form a slurry or paste, and the obtained slurry or paste is applied to a current collector using a doctor blade method or the like, dried, and compacted with a rolling roll or the like to form a positive electrode or a negative electrode There is a method.
前記集電体としては、例えば、インジウム、銅、マグネシウム、ステンレス鋼、チタン、鉄、コバルト、ニッケル、亜鉛、アルミニウム、ゲルマニウム、リチウム、又は、これらの合金等からなる板状体や箔状体等が挙げられる。 Examples of the current collector include plates and foils made of indium, copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, lithium, or alloys thereof. Is mentioned.
なお、結着剤を用いずに、ペレット状に圧密化成形して正極や負極としてもよい。また、負極活物質として金属又はその合金を使用する場合、金属シート（箔）をそのまま負極として使用してもよい。 In addition, it is good also as a positive electrode or a negative electrode by carrying out the consolidation shaping | molding to a pellet form, without using a binder. Moreover, when using a metal or its alloy as a negative electrode active material, you may use a metal sheet (foil) as a negative electrode as it is.
前記固体電解質層は、リチウムイオン伝導率が１０−４Ｓ／ｃｍ以上である無機固体電解質を含有するものである。 The solid electrolyte layer contains an inorganic solid electrolyte having a lithium ion conductivity of 10 −4 S / cm or more.
このような無機固体電解質としては、例えば、非晶質Ｌｉ２Ｓ−Ｐ２Ｓ５及びガラスセラミックス、ＬｉＡｌＴｉＰＯｘ等が挙げられる。 Examples of such an inorganic solid electrolyte include amorphous Li 2 S—P 2 S 5, glass ceramics, LiAlTiPOx, and the like.
本実施形態に係る全固体二次電池は、これらの正極、固体電解質層及び負極の材料を積層し、プレスすることにより製造することができる。 The all-solid-state secondary battery according to the present embodiment can be manufactured by laminating and pressing these positive electrode, solid electrolyte layer, and negative electrode materials.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれら実施例のみに限定されるものではない。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
（実施例１）
一次粒子の平均粒径が１μｍで、二次粒子のメジアン径が１７μｍであるＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２を正極活物質として用いて、固体電解質としてはメカニカルミリング法により合成した非晶質Ｌｉ２Ｓ−Ｐ２Ｓ５（８０−２０ｍｏｌ％）を用い、負極活物質としてはグラファイトを用いた。正負極ともに電極には、活物質と固体電解質、導電材であるＶＧＣＦ（気相成長カーボンファイバ）を６０／３５／５ｗｔ％で混合した合剤を用いた。そして、正極合剤、固体電解質、負極合剤をこの順に積層し、プレスすることにより全固体二次電池を作製した。
Example 1
LiNi 0.8 Co 0.15 Al 0.05 O 2 having an average primary particle diameter of 1 μm and a median diameter of secondary particles of 17 μm was used as the positive electrode active material, and the solid electrolyte was mechanically milled. Synthesized amorphous Li 2 S—P 2 S 5 (80-20 mol%) was used, and graphite was used as the negative electrode active material. For both the positive and negative electrodes, a mixture in which an active material, a solid electrolyte, and VGCF (vapor-grown carbon fiber) as a conductive material were mixed at 60/35/5 wt% was used. Then, a positive electrode mixture, a solid electrolyte, and a negative electrode mixture were laminated in this order and pressed to produce an all-solid secondary battery.
正極活物質の二次粒子のメジアン径は、粒度分布計を用いて測定した粒度分布のＤ５０をもって評価し、また、正極活物質を３ｔ／ｃｍ２の圧力で加圧して、加圧前後の二次粒子のメジアン径（粒度分布のＤ５０）の変化率｛１００−（加圧後Ｄ５０／加圧前Ｄ５０）×１００｝を算出した。 The median diameter of the secondary particles of the positive electrode active material is evaluated based on the D50 of the particle size distribution measured using a particle size distribution meter. Further, the positive electrode active material is pressurized at a pressure of 3 t / cm 2 , The change rate {100− (D50 after pressurization / D50 before pressurization) × 100} of the median diameter (D50 of the particle size distribution) of the secondary particles was calculated.
正極活物質の一次粒子の平均粒径及び分散状態は、走査型電子顕微鏡（ＳＥＭ）によって正極活物質を観察することによって求め、一次粒子の平均粒径は、１００００倍の倍率で１０個以上の二次凝集粒子を選択し、凝集している一次粒子径を見積もった値の平均値として算出した。 The average particle diameter and dispersion state of the primary particles of the positive electrode active material are determined by observing the positive electrode active material with a scanning electron microscope (SEM), and the average particle diameter of the primary particles is 10 or more at a magnification of 10,000 times. Secondary agglomerated particles were selected, and the agglomerated primary particle diameter was calculated as an average value of estimated values.
全固体二次電池の評価は、１Ｃ＝１．４ｍＡとなるように電池を構成し、０．１Ｃ、０．３Ｃ、０．５Ｃ、１Ｃと電流を変化させて放電させて、そのときの０．１Ｃに対する１Ｃの容量維持率によって出力特性を評価した。また、０．１Ｃ充電、０．５Ｃ放電の条件で充放電を１００回実施した際の容量維持率をサイクル維持率とし、これによってサイクル特性を評価した。 The evaluation of the all-solid-state secondary battery was such that the battery was configured so that 1 C = 1.4 mA, and the current was changed to 0.1 C, 0.3 C, 0.5 C, 1 C and discharged, and 0 at that time The output characteristics were evaluated by the capacity retention rate of 1C with respect to 1C. Moreover, the capacity maintenance rate when charging / discharging was performed 100 times under the conditions of 0.1 C charge and 0.5 C discharge was defined as the cycle maintenance rate, and thereby the cycle characteristics were evaluated.
（実施例２）
正極活物質として、一次粒子の平均粒径が１μｍで、二次粒子のメジアン径が６μｍであるものを使用したこと以外は、実施例１と同様にして全固体二次電池を作製し、その電池特性を評価した。
(Example 2)
An all-solid secondary battery was prepared in the same manner as in Example 1 except that a positive electrode active material having an average primary particle diameter of 1 μm and a secondary particle median diameter of 6 μm was used. Battery characteristics were evaluated.
（実施例３）
正極活物質として、一次粒子の平均粒径が０．５μｍで、二次粒子のメジアン径が１０μｍであるＬｉＮｉ０．３３３Ｃｏ０．３３３Ｍｎ０．３３３Ｏ２を使用したこと以外は、実施例１と同様にして全固体二次電池を作製し、その電池特性を評価した。
(Example 3)
Example except that LiNi 0.333 Co 0.333 Mn 0.333 O 2 in which the average particle diameter of primary particles is 0.5 μm and the median diameter of secondary particles is 10 μm was used as the positive electrode active material. All-solid-state secondary batteries were produced in the same manner as in Example 1, and the battery characteristics were evaluated.
（実施例４）
正極活物質として、一次粒子の平均粒径が０．５μｍで、二次粒子のメジアン径が６μｍであるものを使用したこと以外は、実施例３と同様にして全固体二次電池を作製し、その電池特性を評価した。
Example 4
An all-solid secondary battery was prepared in the same manner as in Example 3 except that a positive electrode active material having an average primary particle diameter of 0.5 μm and a secondary particle median diameter of 6 μm was used. The battery characteristics were evaluated.
（実施例５）
正極活物質として、一次粒子の平均粒径が１μｍで、二次粒子のメジアン径が１２μｍであるＬｉＣｏＯ２を使用したこと以外は、実施例１と同様にして全固体二次電池を作製し、その電池特性を評価した。
(Example 5)
As the positive electrode active material, an all-solid secondary battery was produced in the same manner as in Example 1 except that LiCoO 2 having an average primary particle diameter of 1 μm and a secondary particle median diameter of 12 μm was used. The battery characteristics were evaluated.
（比較例１）
正極活物質として、一次粒子の平均粒径が１０μｍで単分散状態のものを使用したこと以外は、実施例５と同様にして全固体二次電池を作製し、その電池特性を評価した。
(Comparative Example 1)
As the positive electrode active material, an all-solid secondary battery was produced in the same manner as in Example 5 except that a monodispersed material having an average primary particle size of 10 μm was used, and its battery characteristics were evaluated.
（比較例２）
正極活物質として、一次粒子の平均粒径が１μｍで単分散状態のものを使用したこと以外は、実施例５と同様にして全固体二次電池を作製し、その電池特性を評価した。
(Comparative Example 2)
As the positive electrode active material, an all-solid secondary battery was prepared in the same manner as in Example 5 except that a monodispersed material having an average primary particle size of 1 μm was used, and the battery characteristics were evaluated.
（比較例３）
正極活物質として、一次粒子の平均粒径が４μｍで単分散状態のＬｉＮｉＯ２を使用したこと以外は、実施例１と同様にして全固体二次電池を作製し、その電池特性を評価した。
(Comparative Example 3)
An all-solid secondary battery was produced in the same manner as in Example 1 except that monodispersed LiNiO 2 having an average primary particle diameter of 4 μm was used as the positive electrode active material, and the battery characteristics were evaluated.
各実施例及び比較例において得られた結果は、表１にまとめて記載した。 The results obtained in each example and comparative example are summarized in Table 1.
実施例１〜５では、全固体二次電池の正極活物質として、一次粒子の平均粒径が１μｍ程度で、二次粒子のメジアン径が５〜２０μｍの凝集粒子からなるものを用いることにより、固体電解質と混合して加圧した際に、一次粒子は変化せずに、二次粒子の凝集が解かれ、固体電解質との空隙に正極活物質が入り込み、正極内部の抵抗を低減させることができた。 In Examples 1 to 5, by using a positive electrode active material of an all-solid secondary battery, the primary particles have an average particle diameter of about 1 μm, and secondary particles have a median diameter of 5 to 20 μm. When mixed with a solid electrolyte and pressurized, the primary particles do not change, the secondary particles are agglomerated, and the positive electrode active material enters the voids with the solid electrolyte, reducing the internal resistance of the positive electrode. did it.
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| WO2012157047A1 (en) * | 2011-05-13 | 2012-11-22 | トヨタ自動車株式会社 | All-solid-state secondary battery |
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